KR20130124947A - Stable granulated agricultural composition - Google Patents

Abstract

The present invention provides a granular pesticide composition having improved stability of an organophosphorus compound as an active ingredient. The present invention relates to a granular pesticide composition containing an organophosphorus compound and calcined clay, wherein said granules contain an organophosphorus compound as an active ingredient, comprising the step of blending calcined clay to improve stability of the active ingredient. The present invention relates to a method for producing a pesticide composition, and a method for improving the stability of the active ingredient contained in the granular pesticide composition, comprising the step of blending calcined clay, and relates to a method wherein the active ingredient is an organophosphorus compound.

Description

Stable Granular Pesticide Composition {STABLE GRANULATED AGRICULTURAL COMPOSITION}

The present invention relates to (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidin-3-ylphosphonothioate (common name: phosphazate) or O-ethyl S-propyl The present invention relates to a granular pesticide composition having improved stability of (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate (common name: imicia force).

Patent Literature 1 discloses an organophosphorus compound exhibiting an effective inhibitory effect against pests, mites and nematodes, and Patent Literature 2 discloses an optically active organophosphorus compound useful as an active ingredient of a preparation for inhibiting harmful animals. In patent documents 1 and 2, organophosphorus compounds can be formulated with various pesticide additives, and clays are described as an example of a carrier in the list of pesticide additives. In addition, Patent Document 3 describes a granule composition used in soil treatment for attaching imicia force to the surface of silicic acid mineral particles having a water content of 0.2% or less and a silicic acid (Si0 ₂ ) content of 90% or more.

Patent Document 1: Japanese Patent Laid-Open No. 63-211293 Patent Document 2: Japanese Patent Laid-Open No. 2-88590 Patent Document 3: Japanese Patent Laid-Open No. 2005-41790

There is no explanation or comment in the art that shows that calcined clay may contribute to the stabilization of phosphazate or imicia force. Phosphate or imicia force (henceforth an organophosphorus compound) may become unstable according to the kind of carrier to be used at the time of manufacture of a granular pesticide composition containing these as an active ingredient. For example, in the case of using the general clay described in the above-described art, sufficient stability of the organophosphorus compound may not be ensured. The present invention provides a granular pesticide composition having improved stability of an organophosphorus compound as an active ingredient.

As a result of various studies to solve the above problems, it has been found that the stability of the organophosphorus compound is improved by using calcined clay in the granular pesticide composition containing the organophosphorus compound as an active ingredient.

That is, the present invention relates to the following (1) to (8):

(1) (a) (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidin-3-ylphosphonothioate or O-ethyl S-propyl (E)-[2 A granular pesticide composition containing (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate and (b) calcined clay;

(2) the composition according to the above (1), containing 0.5 to 30% by weight of component (a) and 70 to 99.5% by weight of component (b);

(3) The composition (1), wherein the component (b) is a composition prepared by calcining clay at a temperature of 900 ~ 1300 ℃;

(4) The composition according to the above (3), wherein the clay is calcined for 15 minutes to 2 hours;

(5) The composition according to the above (1), wherein the component (b) has a water content of 1% by weight or less;

(6) The composition according to (1), wherein component (a) is (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidin-3-ylphosphonothioate;

(7) (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidin-3-ylphosphonothioate or O-ethyl S-propyl (E)-[2- (cya A method for producing a granular agrochemical composition containing noimino) -3-ethylimidazolidin-1-yl] phosphonothioate as an active ingredient, comprising the steps of blending calcined clay to improve the stability of the active ingredient Manufacturing method comprising a; And

(8) A method for improving the stability of the active ingredient, comprising the step of blending calcined clay, wherein the active ingredient is (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazoli Din-3-ylphosphonothioate or O-ethyl S-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate and granular pesticide composition Contained in the method.

According to the present invention, it is possible to obtain a granular pesticide composition having improved stability of an organophosphorus compound as an active ingredient.

In the granular agrochemical composition containing the organophosphorus compound as an active ingredient, by using calcined clay in preparing the organophosphorus compound into a formulation, the stability of the organophosphorus compound is improved.

In the present specification, an "organophosphorus compound" can be prepared according to a known method (for example, Japanese Patent Laid-Open No. 63-211293).

In the present invention, the stability means the chemical stability of the organophosphorus compound, and mainly means the stability when stored as a preparation. The stability at the time of storage can be evaluated by measuring the decomposition rate of an organophosphorus compound after a fixed period, for example under constant storage conditions. Specific examples of the method include the method described in Examples of the present invention.

In the present invention, the term "improved stability" means, for example, that the decomposition rate of a compound which is an active ingredient when using calcined clay is lower than that when using non-fired clay.

In the present invention, the term "granulation" means to granulate the composition so as to belong to a formulation form such as granules and microgranules known in the agricultural arts. For example, the term "granulation" means granulating the composition to have a general particle size of the type of agent.

Examples of calcined clay include those obtained by calcining naturally produced clay, those obtained by calcining commercial clay, and crushed bricks. Since the brick is usually produced by heating at high temperature, the clay in the brick is in a sintered state, and the crushed brick can also be used for producing the granular pesticide composition of the present invention. During the brick making process, defective products often form, such as parts broken. However, since these products are available at low cost, in some cases they are commercially useful.

In the naturally produced clays and commercial clays, the components and properties contained are not always constant in some cases. Even in such a case, in the present invention, by firing clay, undesirable effects on the stability of the organophosphorus compound can be prevented or reduced. Therefore, the granular pesticide composition of the present invention can be produced as a stable granular pesticide composition containing an organophosphorus compound regardless of the type of clay.

Examples of the minerals constituting the clay include montmorillonite, kaolinite, pyrophyllite, bentonite, vermiculite, talc, silica and the like. In the present invention, clay is not understood to be limited to clays derived from the minerals, and various kinds of clays may be used.

Clay produced by molding granular clay or powdered clay may also be used. The clay can be molded according to the preparation method of a formulation known in the agricultural field. For example, the clay can be molded and granulated according to various granulation methods such as extrusion, pan granulation, spray drying, fluidized bed granulation and the like. In the case where the clay is molded and granulated, the particle size of the molded clay is preferably 0.3 to 2 mm, more preferably 0.4 to 1.2 mm.

When molding clays, various additives can be used. Preferred examples of additives are binders such as polyvinyl alcohol, sodium carboxymethyl cellulose, lignin sulfonate, starch, dextrin and gelatin.

When calcining clay, granulated clay may be calcined, or granulated clay may be calcined by molding powdered clay.

The method for producing calcined clay is not prescribed, but is preferably at least 800 ° C, more preferably at 900 to 1300 ° C, even more preferably at 1000 to 1200 ° C, preferably 15 minutes to 2 hours, More preferably, calcined clay may be manufactured by calcining the clay for 30 minutes to 1 hour. However, depending on conditions such as the place where the clay is manufactured, the type of compounding component, and its composition ratio, the temperature and time of firing can be appropriately adjusted, and therefore they should not be understood as being limited to the above range in the present invention.

The composition ratio of the components contained in the calcined clay is not defined as a matter of course. Specifically, a composition having a ratio of 40 to 95% by weight of silicon oxide, 2 to 40% by weight of aluminum oxide and 0.1 to 7% by weight of iron oxide may be mentioned. In the present invention, the binder can be used in the molding of the clay, but since the whole amount of the binder almost disappears during the firing of the clay, it is difficult to define the blending ratio of the binder in the calcined clay. It is also preferable that the amount of water contained in the calcined clay is as small as possible. For example, the water content is preferably adjusted to 1% by weight or less, more preferably 0.2% by weight or less. However, the range often depends on the place where the clay is made and conditions such as the firing temperature and time of the clay, and therefore the water content should not be understood as being limited to the above range in the present invention.

Often, the particle size of calcined clay is appropriately adjusted according to the place of use of the granular pesticide composition, the kind of suppression target, and the like. The particle diameter may be preferably 0.1 to 2 mm, more preferably 0.3 to 1.2 mm. In addition, in the case where the clay is molded into granules and then fired, the particle diameter of the molded particles is preferably 0.3 to 2 mm, more preferably 0.4 to 1.2 mm. However, the particle size of the clay can be appropriately adjusted, and therefore should not be understood as being limited to the above range.

Examples of the preparation of the granular pesticide composition of the present invention include various forms prepared according to various preparation methods in the art. Examples of specific formulation forms include granules, microgranules and the like. Of these, granules are preferred. Granular pesticide compositions can be prepared according to various granulation methods, such as extrusion, pan granulation, spray drying and fluid bed granulation.

Examples of additives that may be used in the preparation of the formulations include various kinds of additives commonly used in the art. The additive is not particularly limited, but examples thereof include surfactants, fillers, binders, stabilizers and the like. Examples of surfactants include nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkylene ethers, polyoxyethylene alkylaryl ethers, polyoxyethylene styrylaryl ethers, polyoxyethylene oleyl ethers, polyoxyethylene fatty acids Esters, polyoxyethylene sorbitan fatty acid esters and polyoxyalkylene block polymers; Anionic surfactants such as alkylarylsulfonic acid salts, dialkylsulfosuccinic acid salts and alkyl phosphate esters; . Examples of binders include polyvinyl alcohol, sodium carboxymethyl cellulose, lignin sulfonic acid salts, starch, dextrin, gelatin and the like.

Although the compounding ratio of each component in the granular pesticide composition of this invention is not prescribed | regulated, it is preferable that the compounding ratio of an organophosphorus compound is 0.5-30 weight%, and it is more preferable that it is 1-15 weight%. It is preferable that it is 70-99.5 weight%, and, as for the compounding ratio of calcined clay, it is more preferable that it is 85-99 weight%. In addition, when various additives are mix | blended, For example, it is preferable that the compounding ratio of surfactant is 0.1-10 weight%, and it is more preferable that it is 0.1-3 weight%. However, the blending ratios can be appropriately adjusted according to the type of the ingredients to be blended, and therefore should not be understood to be limited to the above ranges.

Calcined clay is thought to be able to eliminate the factors that have an undesirable effect on the stability of the organophosphorus compound or to remove the undesirable effects.

For example, since the water content in clay decreases by calcining clay, it is thought that this may contribute to stabilization of the organophosphorus compound. It is also possible that the components in the clay, such as silicon oxide and aluminum oxide, act as catalysts to cause hydrolysis of the organophosphorus compounds or to promote hydrolysis, but organophosphorus compounds may be activated by firing the clay to inactivate its action. Contributions to the stabilization of the compounds are contemplated. In addition, by firing the clay, the specific surface area of each component in the clay is reduced, thereby reducing the likelihood that the components which may have an undesirable effect on the stability of the organophosphorus compound as described above are in contact with each other or the organophosphorus compound. It contributes to the stabilization of organophosphorus compounds.

Example

Examples are described below to further illustrate the present invention, but the present invention should not be construed as being limited thereto.

≪ Example 1 >

(Product preparation)

Powdered clay (trade name: FUBASAMI K clay, BX kaolin or MN clay) and binder (trade name: 5% by weight aqueous solution of CELLOGEN 7A) were kneaded and granulated in an extruder (screen having a diameter of 0.8 mm). Thereafter, the granulated product was dried, sieved, and calcined in an electric furnace for 30 minutes to obtain calcined clay. In addition, granulated clay (trade name: TKR clay) was calcined in an electric furnace for 30 minutes to obtain calcined clay.

Subsequently, 89.58 parts by weight of the calcined clay and 10.42 parts by weight of phosphazate (purity: 96%) were mixed to obtain granules.

Details of each product used in the preparation of the formulation are as follows.

-FUBASAMI K clay: FUBASAMI CRAY CO. LTD manufacture.

-BX kaolin: manufactured by Kanaya Kousan Co., Ltd.

-MN clay: manufactured by NEORAITO KOUSAN CO., LTD.

-TKR clay: manufactured by Anhui Mingmei Minerals Co., Ltd.

-CELLOGEN 7A: Sodium Carboxymethyl Cellulose from DAI-ICHI KOGYO SEIYAKU CO., LTD.

(Stability test)

The granules were placed in sample vials and stored for 4 weeks in a constant temperature chamber set at 54 ° C., and then the granules were analyzed by liquid chromatography to determine the decomposition rate of phosphazate. The results are shown in Table 1 for all kinds of clays and all firing temperatures. In addition, the results in the preparation of the formulations using non-plastic clays are shown together in Table 1.

 Type of clay % Decomposition rate of phoschiate at each firing temperature 900 ℃ 1000 ℃ 1100 ℃ 1200 ℃ Non-plastic  FUBASAMI K clay 7.9 7.3 6.8 6.5 8.7  BX Kaolin - 10.4 5.4 - 19.0  MN clay 2.3 1.5 1.6 - 3.3  TKR clay 22.4 14.5 3.6 3.0 69.2

<Example 2>

Using a crushed granulate of brick (manufactured by Ruijia Cat Litter Products Co., Ltd.), granules of phosphazate were prepared in the same manner as in Example 1 above, and subjected to stability tests. As a result, the decomposition rate of phosphazate was 5.2%.

<Example 3>

FUBASAMI K clay (trade name) was kneaded with water and granulated in an extruder (screen having a diameter of 0.8 mm). Thereafter, the granulated product was dried, sieved, and calcined in an electric furnace (1100 ° C.) for 30 minutes to obtain calcined clay. Using this calcined clay, granules of phosphazate were prepared in the same manner as in Example 1 above, and subjected to stability tests. As a result, the decomposition rate of phosphazate was 6.5%.

<Example 4>

TKR clay (trade name) was calcined for 30 minutes in an electric furnace (1100 ℃) to obtain calcined clay. Subsequently, 94.79 parts by weight of calcined clay and 5.21 parts by weight of phosphazate (purity: 96%) were mixed to obtain granules. Using this granule, a stability test was conducted in the same manner as in Example 1 above. As a result, the decomposition rate of phosphazate was 5.8%.

<Example 5>

TKR clay (trade name) was calcined for 30 minutes in an electric furnace (1100 ℃) to obtain calcined clay. Subsequently, 89.90 parts by weight of calcined clay and 89.90 parts by weight of non-fired TKR clay were mixed with 10.10 parts by weight of imicia force (purity: 99%) to obtain granules. Both granules were each placed in sample vials, stored for 2 weeks in a constant temperature chamber set at 54 ° C., and each granule was analyzed by liquid chromatography to determine the degradation rate of imicia force. As a result, the decomposition rate of imicia force in the granules using non-plastic TKR clay was 43.3%, while the decomposition rate of imisia force in the granules using calcined TKR clay was 8.5%.

<Examples 6 to 11>

According to Example 1, the granules were prepared with the compounding ingredients and the compounding ratios shown in Table 2. A stability test is performed to confirm that the active ingredients exhibit good stability.

The detail of surfactant used for preparation of a formulation is as follows.

NOIGEN EA-177: polyoxyethylene distyrylphenyl ether (manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD)

-LAMIGEN ES-60: polyoxyethylene lanolin fatty acid ester (manufactured by DAI-ICHI KOGYO SEIYAKU CO., LTD)

Compounding ingredients
 Compounding ratio (part by weight)  Example 6 7 8 9 10 11
Active ingredient
Phoschiate
(96% purity) 1.05 15.62 5.21 10.21 - - Imicia Force
(99% purity) - - - - 1.01 15.15
Calcined clay


FUBASAMI K clay 98.95 - - - 98.99 - BX Kaolin - 84.38 - - - 84.85 MN clay - - 94.69 - - - TKR clay - - - 86.79 - - Surfactants
NOIGEN EA-177 - - 0.1 - - - LAMIGEN ES-60 - - - 3.0 - -

While the invention has been described in detail with reference to specific embodiments thereof, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.

This application is based on the JP Patent application (Japanese Patent Application No. 2010-239413) filed on October 26, 2010, The content is taken in here as a reference. All references cited herein are incorporated herein in their entirety.

According to the present invention, it is possible to obtain a granular pesticide composition having improved stability of an organophosphorus compound as an active ingredient.

Claims (8)

(a) (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidin-3-ylphosphonothioate or O-ethyl S-propyl (E)-[2- (cya A granular agrochemical composition containing noimino) -3-ethylimidazolidin-1-yl] phosphonothioate and (b) calcined clay. The composition of claim 1 containing 0.5 to 30 weight percent of component (a) and 70 to 99.5 weight percent of component (b). The composition of claim 1 wherein component (b) is prepared by calcining clay at a temperature of 900-1300 ° C. The composition of claim 3 wherein the clay is calcined for 15 minutes to 2 hours. The composition of claim 1 wherein component (b) has a water content of 1 wt% or less. The composition of claim 1, wherein component (a) is (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidin-3-ylphosphonothioate. (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidin-3-ylphosphonothioate or O-ethyl S-propyl (E)-[2- (cyanoimino) A method for producing a granular pesticide composition containing 3-ethylimidazolidin-1-yl] phosphonothioate as an active ingredient, comprising the step of blending calcined clay to improve the stability of the active ingredient. Manufacturing method. A method of improving the stability of an active ingredient, comprising the step of blending calcined clay, wherein the active ingredient is (RS) -S-sec-butyl O-ethyl 2-oxo-1,3-thiazolidine-3 -Ylphosphonothioate or O-ethyl S-propyl (E)-[2- (cyanoimino) -3-ethylimidazolidin-1-yl] phosphonothioate and is contained in the granular agrochemical composition That way.